Diarylselenocarbazone compounds

ABSTRACT

WHEREIN A IS AN ARYL RADICAL CONTAINING FROM 6 TO ABOUT 12 CARBON ATMOS AND X, Y AND Z ARE INDIVIDUALLY SELECTED FROM THE GROUP CONSISTING OF HYDROGEN, LOWER ALKYL, HYDROXY, HALO, NITRO, AMINO, DI-LOWER ALKYLAMINO OR PHENYLAZO.   X-A(-Y)(-Z)-N=N-C(=SE)-NH-NH-A(-X)(-Y)-Z   A NEW CLASS OF DIARYLSELENIUM COMPOUNDS ARE PROVIDED WHICH HAVE THE FOLLOWING GENERAL FORMULA:

United States Patent 3,804,822 DIARYLSELENOCARBAZONE COMPOUNDS JohnKazan, Jr., Somerville, N.J., assignor to American Cyanamid Company,Stamford, Conn.

No Drawing. Continuation-impart of application Ser. No. 853,506, Aug.27, 1969, now Patent No. 3,575,872, dated Apr. 20, 1971. Thisapplication Jan. 27, 1971, Ser. No. 110,334

Int. Cl. C07c 107/00 US. Cl. 260-149 2 Claims ABSTRACT OF THE DISCLOSUREA new class of diarylselenium compounds are provided which have thefollowing general formula:

wherein A is an aryl radical containing from 6 to about 12 carbon atomsand x, y and z are individually selected from the group consisting ofhydrogen, lower alkyl, hydroxy, halo, nitro, amino, di-lower alkylaminoor phenylazo.

CROSS REFERENCE TO A RELATED PATENT APPLICATION This application is acontinuation-in-part of US. applica tion Ser. No. 853,506, filed on Aug.27, 1969, issued as US. Pat. No. 3,575,872 on Apr. 20, 1971.

Generally stated the subject matter of the present invention relates toa new class of selenium compounds. More particularly, the inventionrelates to a new class of diarylselenium compounds which find utility asintermediates in the preparation of particular photochromicselenocarbazonate compounds.

BACKGROUND OF THE INVENTION Photochromic compounds have heretofore beenapplied to or incorporated in various substrates to render saidmaterials photochromic. For example, polymers containing a measurablequantity of photochromic compound change color upon exposure to visibleradiation. This color change is believed to follow from thetransformation of the photochromic compound from a stable form to ameta-stable form. When the source of radiation is removed, the compoundreturns from the meta-stable to the stable form and reverts to itsoriginal color. Materials of this type are useful in obtaining uniquecamouflage, design, and novelty effects. Many photochromic compositionsheretofore available have met with limited acceptance because of theirrelatively slow rates of conversion by light into their meta-stable form(highly colored forms) and/or their slow rate of return to their stable(original color) form.

The advent of a new class of selenium photochromic compounds; namely,the 1,5-diarylselenocarbazonates and the metal complexes of1,S-diarylselenocarbazonates, has resulted in filling a long standingneed.

The present invention represents the culmination of a series ofinvestigations conducted largely by the inventor and his associates,directed to the preparation of such new photochromic compounds.

It is a primary object of the invention then to provide precursors orintermediates to such photochromic compounds.

3,804,822 Patented Apr. 16, 1974 "Ice Additional objects and advantagesof the invention will be set forth in part in the description whichfollows and THE INVENTION To achieve the foregoing object, and inaccordance with its purpose, as embodied and broadly described, thepresent invention relates to a diarylselenium compound of the formula:

wherein R is N=N or NHNH-, A is an aryl radical containing from 6 toabout 12 carbon atoms and x, y and z are individually selected from thegroup consisting of hydrogen, lower alkyl, hydroxy, halo, nitro, amino,dilower alkylamino or phenylazo.

The invention consists of the novel materials and processes herein shownand described. In addition, it should also be understood that both theforegoing general description and the following detailed description areexemplary and explanatory and are not restrictive of the invention.

The 1,5-diarylselenocarbazones (I) intermediates can readily be preparedby heating the corresponding 2-arylhydrazonium 3-aryldiselenocarbazates(II) to form the corresponding diarylselenocarbazides (III) which can bereadily oxidized to the diarylselenocarbazones (I). This can beillustrated by the following equation:

(III) /N=N AT 1] N H-NH- AT The 2-arylhydrazonium3-aryldiselenocarbazates (II) can be prepared by reacting thecorresponding arylhydra- Representative arylhydrazines (IV) which can beemployed include phenylhydrazine, p-tolylhydrazine, 2,4- xylylhydrazine,l-naphthylhydrazine, Z-naphthylhydrazine, p-nitrophenylhydrazine,m-methoxyphenylhydrazine, p-chlorophenylhydrazine, 1bromo-2-naphthylhydrazine, p-hydrazinobenzoic acid,p-hydrazinoN,N-dimethylbenzamide, 4'-hydrazinoacetanilide and the like.

The arylhydrazine and carbon diselenide can be reacted in stoichiometricamounts in a suitable inert solvent such as dichloromethane or absoluteethanol. The reaction temperature can range from about to about 30 C.The 2-arylhydrazonium S-aryldiselenocarbazates (II) can be isolated byconventional procedures.

The conversion of the 2-arylhydrazonium 3-aryldiselenocarbazate (H) tothe corresponding selenocarbazide (III) can be conveniently effected byheating the hydrazonium salt. This can be done by refluxing a solutionof the hydrazonium salt in a suitable inert solvent, such as ethylacetate or carbon tetrachloride, until there is no further evolution ofhydrogen selenide. Purification of the crude product is unnecessarybefore carrying out the conversion of said selenocarbazide to the1,5-diarylselenocarbazone (I). It is considered preferable, however, toremove the solvent before proceeding with the conversion to the1,S-diarylselenocarbazone.

The diarylselenocarbazide (III) can be converted to the1,S-diarylselenocarbazone (I) by oxidation with atmospheric oxygen in analkaline medium. The oxidation can be conveniently accomplished byadding an alkali, such as for example potassium hydroxide, sodiumhydroxide, lithium hydroxide and the like, and an inert solvent, such asethanol, methanol and the like, to the selenocarbazide, followed byagitation in the presence of atmospheric oxygen at a low temperature,e.g., 50" to about C. The resulting 1,5-diarylselenocarbazone can beisolated by adding the reaction mixture to an aqueous mineral acid toprecipitate the product. The product can be recovered by filtering orother conventional techniques.

The following examples are provided for illustrative purposes and mayinclude particular features of the invention. However, the examplesshould not be construed as limiting the invention, many variations ofwhich are possible without departing from the spirit or scope thereof.

EXAMPLEI Preparation of 2-phenylhydrazonium 3-phenyldiselenocarbazate Asolution of 3.4 g. carbon diselenide in 90 g. dichloromethane is slowlyadded to a solution of 11.0 g. phenylhydrazine in 350 g.dichloromethane. After the mixture is stirred for an additional 1-2hours, the resulting crystalline precipitate is separated by filtrationand washed with dichloromethane. The product melts at about 67 C. withdecomposition.

Calc. for C H N Se (percent): C, 40.4; H, 4.17; N, 14.5; Se, 40.8. Found(percent): C, 40.1; H, 4.15; N, 14.8; Se, 40.0.

When the procedure is repeated substituting for the phenylhydrazineequivalent amounts of p-tolylhydrazine, Z-naphthylhydrazine,p-nitrophenylhydrazine, p-fluorophenylhydrazine or4-hydrazinoacetanilide, the products obtained are 2-p-tolylhydrazonium3p-tolyldiselenocarbazate,

2-(2-naphthyl) hydrazonium 3-(2-naphthyldiselenocarbazate,

2-p-nitropheny1hydrazonium '3-p-nitrophenyldiselenocarbazate,

2-p-fluoropheny1hydrazonium 3-p-fluorophenyldiselenocarbazate, and

Z-pacetamidophenylhydrazonium 3-pacetamidophenyldiselenocarbazate,

respectively.

EXAMPLE H Preparation of 1,S-diphenylselenocarbazone A solution of 3.0g. 2 phenylhydrazonium 3-phenyldiselenocarbazate (product of Example 1)in 150 ml. ethyl acetate is refluxed until the evolution of hydrogenselenide has ceased. The solution is cooled and filtered, and thesolvent is removed by evaporation. The resulting brown oil is stirredfor about one hour at l0 C. with 50 ml. 10% solution of potassiumhydroxide in methanol, and the red mixture is poured into 200 ml. 2 Nsulfuric acid, and saturated with sodium chloride at 5 C. Theprecipitate is separated by filtration, washed with water and dried atroom temperature. The material is extracted in a Soxhlet apparatus withpentane. The product is obtained from the pentane as a brown solidmelting at 65- 70 C. with decomposition.

Calc. for C H N Se (percent): C, 51.5; H, 3.99; N, 18.5; Se, 26.0. Found(percent): C, 51.5; H, 4.10; N, 17.4; Se, 26.2.

When the above procedure is repeated substituting for the 2phenylhydrazonium 3 phenyldiselenocarbazate equivalent amounts of 2 ptolylhydrazonium 3 ptolylselenocarbazate, 2 (2 naphthyl) hydrazonium 3-(2 naphthyl) diselenocarbazate, 2 p nitrophenylhydrazinium 3 pnitrophenyldiselenocarbazate, Z-p-fiuorophenylhydrazonium 3 pfluorophenyldiselenocarbazate or 2 p acetamidophenylhydrazonium3-p-acetamidophenyldiselenocarbazate, the products obtained are 1,5-di-ptolyselenocarbazone, 1,5 di (2 naphthyl) selenocarbazone, 1,5 di pnitrophenylselenocarbazone, 1,5 di p fiuorophenylselenocarbazone and1,5-di-pacetamidophenylselenocarbazone, respectively.

What is claimed is:

1. A diarylselenium compound of the formula:

L N=N-- n+1, Se=C J 14 NH-NH- n+1:

wherein A is aryl containing from 6 to 12 carbon atoms and x, y and zare individually selected from the group consisting of hydrogen, loweralkyl, halo and nitro.

2. The diarylselenocarbazone l,5-diphenylselenocarbazone.

References Cited UNITED STATES PATENTS 3,359,254 12/1967 Kazan 260-4493,575,872 4/1971 Kazan 260-193X OTHER REFERENCES Heilbron: Dictionary ofOrganic Compounds, vol. 3, New York, Oxford University Press, 1965, pp.1277 and 1298.

LEWIS GOTTS, Primary Examiner C. F. WARREN, Assistant Examiner US. Cl.X.R.

WWW ZDATENT @FFEQE @TERYTWECATE (J-F FJEQEN Patent NCLZJ 650L822 M Anril16. 197

Inventofls). John Kazan, Jr

It is certified that error appears in the a'bove-identified patent amithat said Letters Patent are hereby corrected as shown below:

4 C010 1, line 6 l,B-Qiarylselenocalrbanzanates" snould read vl,5-diarylselenocarbazones Col. line 55: ddc'aziniurri" should readdrazonium Signed and sealed this 10th day of September 197 (SEAL)At'test:

MCCGYM- GIB ON; JR. c iARsHALL DANN Attesting Office? Commissioner'bfPatents

